CN1107706C - Heavy oil and residual oil hydrogenating conversion process - Google Patents
Heavy oil and residual oil hydrogenating conversion process Download PDFInfo
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- CN1107706C CN1107706C CN 00110716 CN00110716A CN1107706C CN 1107706 C CN1107706 C CN 1107706C CN 00110716 CN00110716 CN 00110716 CN 00110716 A CN00110716 A CN 00110716A CN 1107706 C CN1107706 C CN 1107706C
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003921 oil Substances 0.000 title abstract description 70
- 239000000295 fuel oil Substances 0.000 title abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000007667 floating Methods 0.000 claims description 25
- 238000005516 engineering process Methods 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012053 oil suspension Substances 0.000 claims 4
- 239000000725 suspension Substances 0.000 abstract description 34
- 239000000571 coke Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000002010 green coke Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- -1 carbonyl metal compounds Chemical class 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a hydrogenation conversion method of heavy oil and residual oil. Low temperature hydrogenation conversion is first carried out to reaction raw materials in a suspension bed or a similar reactor for a long time; then, high temperature hydrogenation conversion is carried out in the suspension bed or the similar reactor for a short time. A raw material of residual oil enhances the H/C ratio of the residual oil by the hydrogenation pretreatment of a first stage suspension bed; besides, asphaltene of the residual oil is better dispersed in colloidal suspension; thus, the coke formation rate of a reaction is reduced when the high temperature hydrogenation conversion of the suspension bed is carried out to the residual oil. The operating life of a hydrogenation device of residual oil of the suspension bed is realized under high conversion rate, and the industrial operating requirement is achieved.
Description
The present invention relates to weight, residual oil treatment process.Specifically, the present invention relates to a kind of two sections suspension bed high conversion residual hydrogenation methods.This technology is at first carried out the long-time hydrocracking of low temperature in suspension bed or similar reactor, and then carries out hydrocracking between high temperature, short time in suspension bed or similar reactor.
Along with the exploitation of heavy crude and the variation of product demand, crude oil deep processing technology becomes the emphasis of world today petroleum refining industry exploitation.The key of heavy crude deep processing and heavy oil lighting is the hydrogen richness that increases in the heavy oil, and removes the impurity such as sulphur, nitrogen and heavy metal in the heavy oil.Aspect improving the heavy oil conversion degree of depth and improving the clean or white quality, the heavy-oil hydrogenation transformation technology is one of main method, it not only can slough detrimental impurity such as metal in the residual oil, sulphur, nitrogen in a large number, the low boiling component that can also make heavily, slag oil crack becomes high value.
At present, the Residue Hydrotreating Technology of industrialization or technology maturation has fixed bed, moving-bed, ebullated bed and suspension bed four big classes in the world, wherein fixed-bed process is used wider, also the most ripe, but this technology has strict restriction to stock oil, contain a large amount of impurity particularly during the inferior heavy oil of carbon residue and metal in processing, beds easily stops up.Though and moving-bed and ebullated bed technology can be processed inferior heavy oil, invest higher.The working pressure of suspension bed technology is low, air speed is high, invests also lowlyer, and can be used for the lighting of inferior heavy oil.Therefore each major oil companies is is all competitively researching and developing suspension bed hydrogenation process.
The raw material that suspension bed residual oil hydrogenation technology is processed is heavy, residual oil.And residual oil is the very complicated mixture of a kind of composition, except that containing impurity such as a large amount of S, N, heavy metal, also contains colloid and bituminous matter.Wherein bituminous matter is to contain heteroatoms and have high polarity macromolecule compound, Pfeiffer﹠amp; Sal model description bituminous matter is: around bituminous matter gelatinous layer or high boiling point polar aromatics are arranged, and bituminous matter is stabilized in the soliquid.Lacking under the situation that colloid or colloid diluted by the paraffinic hydrocarbon molecule, these bituminous matters itself are with regard to coalescent or flocculation, thereby form macromole, just are precipitated out from solution, and this is the first step of coking process.Facing under the hydrogen environment, there is a kind of proneness that is converted into light paraffins and aromatic hydrocarbons in bituminous matter; Polar aromatics also is converted into light component, but its speed is faster than bituminous matter.The result is, with the carrying out of reaction, polar aromatics and bitum ratio are reducing, and the ratio of paraffinic hydrocarbon and aromatic hydrocarbons causes bituminous matter to be flocculated increasing at last, and intermediate phase forms, consequently generation coking at last of precipitation.Therefore concerning the suspension bed residual oil hydrogenation that faces the hydrogen heat cracking reaction, residual oil is easy to green coke.In addition, the residual oil coking yield in the suspension bed residual oil hydrogenation device also increases with the raising of bottoms conversion.The cost that obtains the residual oil high conversion is to generate a large amount of coke.As a result, the reactor of suspension bed residual oil hydrogenation device can be stopped up by coke usually, makes device shortening running period, the requirement that does not reach industrial operation.For improving suspension bed residual oil hydrogenation technology, each major oil companies has all developed own corresponding patented technology.Make the additive of device after the VCC process using brown coal of Germany VEBA company exploitation or coke are levigate.Related to the scorch retarder that is used for suspension bed technology among relevant patent US4299685, the CA1276902 of CANMET technology application, US4999328, CN1035836, the CN1042174: coal dust, coking coal powder and ferric sulfate, iron coal paste and the ultrafine iron sulphate of flue dust, load Fe, Co, metal-salts such as Mo, Zn.The CN87107363 patent of Japanese publication has related to suspension bed disperse type catalyzer and the corresponding tubular reactor of being made by molybdenum compound, carbon black and hydrocarbon ils.The HDH technology of Venezuela INTEVEP company research and development is to make catalyzer with the natural mineral fine powder that contains Ni, V.The U54067799 patent proposition of Exxon company application cooperates with the phthalocyanine cobalt with ferric oxide carries out suspension bed residual oil hydrogenation.The Aurabon technology of Uop Inc. is to adopt the finely powdered vanadium sulfide to make catalyzer, and thousand Dai Tian companies are used for residual oil with the useless HDS catalyst fines of industry to press floating bed hydrogenation.Above-mentioned suspension bed technology is the floating bed hydrogenation technology of using solid catalyst.US4226742, the US4134825 of Exxon company application related to naphthenate or the soap cooperation is used for suspension bed residual oil hydrogenation.Patent CA2004882 has proposed elder generation charging residual oil has been diluted as thinner with 200～455 ℃ of distillates, thinning ratio is 10～1: 1, adds the heavy oil floating bed hydrogenation scheme (HC) that carbonyl metal compounds such as many cobalt-carbonyls or molybdenum, nickel, iron carry out hydrotreatment then
3Texaco company proposes to use C at patent US4125455
7～12Lipid acid molybdenum or tungsten make catalyzer, IFP then proposes to cooperate with cobalt naphthenate with molybdenum naphthenate in patent US4285804, and the tail oil that will be rich in metal circulates.US4557821, US4710486, US4762812, US4824821, US4857496, the US4970190 patent of Chevron company application related to preparation, dehydration, sulfuration and the use of ammonium molybdate water-soluble catalyst and fat liquor thereof.In these methods, all be to come the inhibited reaction coking by changing the catalyzer or the additive that use in the suspension bed hydrogenation process, when but suspension bed residual oil hydrogenation technology turned round under the condition of higher bottoms conversion at present, the reactor coking was still very serious, and the device steady running time is shorter.Therefore, need a kind of processing method of can not having remarkable coke generation in the high conversion operation in the art.
For reaching above-mentioned purpose, the invention provides a kind of heavy, residual hydrocracking process integration, it has not only remedied the deficiency of existing suspension bed residual oil hydrogenation technology, but also has satisfied the needs that crave for for a long time this area.
The object of the present invention is to provide a kind of method for transformation of two sections hydrogenation of residual oil suspended bed, the floating bed hydrogenation hydrogenation unit is turned round under higher conversion, and the amount of coke that reaction generates is less.
Purpose of the present invention reaches by following measure: weight, residual oil reaction raw materials are at first under the condition that hydrogen exists, enter first section low temperature long residence time floating bed hydrogenation device and carry out pre-treatment, reaction effluent directly enters second section high temperature short residence time(SRT) floating bed hydrogenation device and carries out the high conversion reaction, described reaction raw materials pretreated processing condition in first section low temperature long residence time floating bed hydrogenation device are: temperature of reaction is 340-400 ℃, reaction pressure is 8.0-17.0MPa, and volume space velocity is 0.2-0.7h during liquid
-1, hydrogen to oil volume ratio is 500-1500; First section floating bed hydrogenation device reaction effluent carries out the high conversion reaction in second section high temperature short residence time(SRT) floating bed hydrogenation device processing condition are: temperature of reaction is 390-470 ℃, reaction pressure is 8.0-17.0MPa, and volume space velocity is 0.5-20h during liquid
-1, hydrogen to oil volume ratio is 500-1500; Wherein carry out the high conversion temperature of reaction than high 10-100 ℃ of first section low temperature long residence time floating bed hydrogenation device pretreatment reaction temperature, the high 0.2-19h of volume space velocity during liquid in second section high temperature short residence time(SRT) floating bed hydrogenation device
-1
Two sections suspension bed residual oil hydrogenation devices of the present invention all can adopt catalyzer or additive, also can not adopt catalyzer or additive, and two section apparatus both can use with a kind of catalyzer, also can use different catalyzer.If adopt catalyzer or additive, can use any catalyzer or additive that is applicable to that hydrogenation of residual oil suspended bed transforms, both can be the catalyzer of sulfide deposition on aluminum oxide or silica-alumina supports of solid powder th-1 catalyst such as Co, Mo or Ni; It also can be disperse type catalyzer, comprise oil-soluble catalyst and water-soluble catalyst, for example, oil-soluble catalyst has iron cpd and coal dust are ground made iron-coal paste shape catalyzer in oil, water-soluble catalyst such as molybdenum phosphate aqueous solution catalyzer, Mo, Ni, P water-soluble catalyst etc.Wherein, better with the catalyst effect of decentralized, in disperse type catalyzer, the present invention preferentially recommends water-soluble catalyst, a kind of Mo2-15w% that contains of special recommendation, Ni content is 0.1-2w%, P content is the aqueous solution catalyzer (referring to Chinese patent CN1062621A) of 0.1-3w%.
Described pretreatment technology condition is preferably: temperature of reaction is 350-390 ℃, and reaction pressure is 8.0-15.0MPa, and volume space velocity is 0.5-0.6h during liquid
-1, hydrogen to oil volume ratio is 800-1500.
Described high conversion reaction process condition is preferably: temperature of reaction is 410-460 ℃, and reaction pressure is 8.0-15.0MPa, and volume space velocity is 1.0-15h during liquid
-1, hydrogen to oil volume ratio is 800-1500.
Described second section high conversion temperature of reaction be than first section best high 30-80 of pretreatment reaction temperature ℃, the best high 0.5-15h of volume space velocity during liquid
-1
Polycondensation own produces because the green coke in the thermal cracking residue is not a bituminous matter, but (petroleum journal (refining of petroleum) 1995,1,61～65) that bituminous matter generates when being separated into phase independently from oil solution.Therefore, suspension bed residual oil hydrogenation technology transform residual oil and not the condition of green coke be that enough polar aromatics are arranged in the residual oil, could guarantee that residual oil does not make bituminous matter flocculate when facing the hydrogen heat cracking reaction, formation intermediate phase, green coke at last.In addition, experimental study shows, when low invert point, cracking reaction mainly takes place in the residual oil thermal transition, and it is less that condensation reaction is carried out, and the structural parameter of resultant show that also the variation of aromatic hydrocarbons virtue nuclear in reaction is little, and its principal reaction is the fracture of side chain.The fracture of colloid possibility generating unit sheet and the fracture and the less condensation reaction of alkyl group side chain, virtue-alkyl structure takes place in bituminous matter too, the cracking of ring-alkyl structure and alkyl group side chain generates volatile matter-alkane, aromatic hydrocarbons (single, double Polycyclic aromatic hydrocarbons), alkene, naphthenic hydrocarbon (single, double ring naphthenic hydrocarbon) and non-volatile product-aromatic substance.So, residual oil is through after the low temperature conversion, its polar aromatics content increases, and asphalt content reduces, polar aromatics/bitum ratio is increased, and react and under hydro condition, carry out, increased the H/C ratio of residual oil simultaneously again, strong cracking reaction when residual oil carries out pyrolytic conversion reduces its green coke reaction.Document (international heavy oil, residua upgradings in 1992 and utilize Conference Papers collection (Chinese edition), 54～58) has also proved residual oil in low cracking temperature, and long reaction time helps reducing the generation of coke precursors.Therefore, first section low temperature long residence time floating bed hydrogenation device of the present invention is mainly the residual oil that second section high temperature short residence time(SRT) floating bed hydrogenation device of the present invention provides high polar aromatics/bituminous matter and H/C ratio, prevents residual oil a large amount of green cokes in second section high temperature short residence time(SRT) floating bed hydrogenation device.
In the suspension bed residual oil hydrogenation device, high bottoms conversion correspondence be high temperature of reaction and long reaction time, but high cracking temperature and long reaction time easily make reaction generate a large amount of coke.Therefore, second section floating bed hydrogenation of the present invention is high temperature, the hydrogenation technique of the short reaction residence time.
The present invention is applicable to normal slag and the hydrocracking that subtracts slag, and the residual hydrogenation high conversion that is particularly useful for high metal, high carbon residue, high condensed ring material, high nitrogen-containing transforms.
Compared with prior art, characteristics of the present invention are: residual oil raw material is by first section floating bed hydrogenation pre-treatment, not only improved the H/C ratio of residual oil, and the bituminous matter in the residual oil also better is dispersed in the soliquid, make residual oil when carrying out the conversion of high temperature floating bed hydrogenation, the reaction coking yield has reduced, and has realized the running life under the suspension bed residual oil hydrogenation technology high conversion, reaches the industrialization running requirements.
Fig. 1 has shown joint process figure of the present invention.
Further specify the present invention below in conjunction with drawings and Examples.
Raw material residual oil 1 is with after recycle hydrogen 2 mixes, mix with catalyzer or additive 5 again and enter first section suspension bed residual oil hydrogenation pretreatment reaction device 3 jointly, enter second section high temperature suspension bed residual oil hydrogenation reactor 7 after residual oil 4 and replenishment cycles hydrogen 6 mix after the pre-treatment, floating bed hydrogenation generates and enters downstream separation system after oil 8 leaves suspended-bed reactor, after purifying, hydrogen-rich gas after the separation returns the reactive system of process integration, liquid-phase product enters the system of re-refining separately or enters the common system of re-refining after fractionation, carry out fractionation again.
For further specifying all main points of the present invention, enumerate following examples.
Embodiment 1～4 comparative example 1～2
Below in the test of Jie Shaoing, suspension bed residual oil hydrogenation technology is the catalyzer of this test with the 9 prepared catalyzer of embodiment among the patent CN1045307C, this catalyzer is a water-soluble catalyst, and it contains Mo is that 5.6w%, Ni are that 0.7w%, P/Mo atomic ratio are 0.087.The catalyzer usage quantity is 300ppm.The stock oil character of using sees Table-1.The operational condition and the reaction result table-2 of test.
Table-1 stock oil main character
| Project | Data |
| Density (20 ℃) g/cm 3 | 0.9829 |
| The H/C atomic ratio | 1.61 |
| Stable hydrocarbon, w% | 30.3 |
| Aromatic hydrocarbon, w% | 25.8 |
| Colloid, w% | 40.9 |
| Bituminous matter, w% | 3.0 |
The operational condition and the reaction result of table-2 tests
| Embodiment or comparative example | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| First section long-time suspension bed residual oil hydrogenation of low temperature | ||||||
| Temperature of reaction, ℃ | 360 | 370 | 380 | 390 | ||
| Air speed, h -1 | 0.5 | 0.5 | 0.6 | 0.6 | ||
| Hydrogen pressure, Mpa | 10.0 | 12.0 | 14.0 | 15.0 | ||
| Hydrogen-oil ratio | 800 | 1000 | 1200 | 1500 | ||
| Generate oil nature | ||||||
| The H/C atomic ratio | 1.61 | 1.61 | 1.62 | 1.64 | 1.67 | 1.68 |
| Stable hydrocarbon, w% | 30.3 | 30.3 | 37.5 | 38.6 | 39.9 | 41.5 |
| Aromatic hydrocarbon, w% | 25.8 | 25.8 | 25.0 | 24.7 | 24.5 | 23.7 |
| Colloid, w% | 40.9 | 40.9 | 36.5 | 35.9 | 35.1 | 34.5 |
| Bituminous matter, w% | 3.0 | 3.0 | 1.0 | 0.8 | 0.5 | 0.3 |
| Suspension bed residual oil hydrogenation between second section high temperature, short time | ||||||
| Temperature of reaction, ℃ | 410 | 410 | 420 | 430 | 440 | 450 |
| Air speed, h -1 | 1.0 | 1.0 | 5.0 | 8.0 | 10.0 | 12.0 |
| Hydrogen pressure, Mpa | 8.0 | 10.0 | 10.0 | 12.0 | 14.0 | 15.0 |
| Hydrogen-oil ratio | 800 | 800 | 1000 | 1000 | 1200 | 1500 |
| Reaction result | ||||||
| Generate oily coke content, w% | 0.37 | 0.25 | 0.05 | 0.03 | 0.01 | 0.01 |
| The AGO productive rate | 30.2 | 28.2 | 34.5 | 38.7 | 43.2 | 47.1 |
| The VGO productive rate | 28.7 | 30.1 | 37.1 | 40.6 | 43.9 | 46.3 |
Claims (8)
1, a kind of heavy, residuum hydroconversion method, it is characterized in that reaction raw materials is at first under the condition that hydrogen exists, enter first section low temperature long residence time floating bed hydrogenation device and carry out pre-treatment, reaction effluent directly enters second section high temperature short residence time(SRT) floating bed hydrogenation device and carries out the high conversion reaction, described reaction raw materials pretreated processing condition in first section low temperature long residence time floating bed hydrogenation device are: temperature of reaction is 340-400 ℃, reaction pressure is 8.0-17.0MPa, and volume space velocity is 0.2-0.7h during liquid
-1, hydrogen to oil volume ratio is 500-1500; First section floating bed hydrogenation device reaction effluent carries out the high conversion reaction in second section high temperature short residence time(SRT) floating bed hydrogenation device processing condition are: temperature of reaction is 390-470 ℃, reaction pressure is 8.0-17.0MPa, and volume space velocity is 0.5-20h during liquid
-1, hydrogen to oil volume ratio is 500-1500; Wherein carry out the high conversion temperature of reaction than high 10-100 ℃ of the-section low temperature long residence time floating bed hydrogenation device pretreatment reaction temperature, the high 0.2-19h of volume space velocity during liquid in second section high temperature short residence time(SRT) floating bed hydrogenation device
-1
2,, it is characterized in that described pre-treatment carries out in the presence of heavy, dreg-oil suspension bed catalyzer according to described heavy, the residuum hydroconversion method of claim 1.
3,, it is characterized in that the reaction of described high conversion carries out in the presence of heavy, dreg-oil suspension bed catalyzer according to described heavy, the residuum hydroconversion method of claim 1.
4, according to described heavy, the residuum hydroconversion method of claim 1, it is characterized in that described pretreatment technology condition is: temperature of reaction is 350-390 ℃, and reaction pressure is 8.0-15.0MPa, and volume space velocity is 0.5-0.6h during liquid
-1, hydrogen to oil volume ratio is 800-1500.
5, according to described heavy, the residuum hydroconversion method of claim 1, it is characterized in that described high conversion reaction process condition is that temperature of reaction is 410-460 ℃, reaction pressure is 8.0-15.0MPa, volume space velocity is 1.0-15h during liquid
-1, hydrogen to oil volume ratio is 800-1500.
6,, it is characterized in that described second section high conversion temperature of reaction than first section high 30-80 of pretreatment reaction temperature ℃, the high 0.5-15h of volume space velocity during liquid according to described heavy, the residuum hydroconversion method of claim 1
-1
7,, it is characterized in that described heavy, dreg-oil suspension bed catalyzer is a disperse type catalyzer according to claim 2 or 3 described heavy, residuum hydroconversion methods.
8, according to claim 2 or 3 described heavy, residuum hydroconversion methods, it is characterized in that described heavy, dreg-oil suspension bed catalyzer is to contain Mo2-15w%, Ni content is 0.1-2w%, P content is the aqueous solution catalyzer of 0.1-3w%.
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| CN 00110716 CN1107706C (en) | 2000-07-24 | 2000-07-24 | Heavy oil and residual oil hydrogenating conversion process |
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